The acetic acid corrosion resistance of silver electrodes is critical for ensuring photovoltaic (PV) module reliability. Ethylene-vinyl acetate (EVA) is the most widely used encapsulant material in photovoltaic modules. Under exposure to light, heat, and moisture, EVA decomposes to generate acetic acid, which corrodes the silver electrodes, leading to energy conversion efficiency degradation of the module. To address this problem, the lead-free paste was formulated and evaluated in this paper to improve the anti-acetic acid performance. The contact resistivity of the front and the rear side of the solar cells have been measured before and after acetic acid exposure, and greater degradation is shown in the front electrode than in the rear side. Furthermore, the lead-free paste demonstrates lower efficiency degradation compared to the lead-containing paste after acetic acid exposure. In addition, top-view and cross-sectional scanning electron microscopy was performed to analyze the mechanism of the acetic acid corrosion resistance, in which the silver acetate particles were observed. Our experimental results demonstrate that the lead-free paste exhibits superior acetic acid corrosion resistance, which is due to its higher glass acidity and the absence of lead oxide that causes enhanced chemical reactivity with acetic acid. Based on these findings, the acetic acid corrosion model is proposed to attribute the conversion efficiency degradation of reactions between acetic acid and silver, as well as the glass of the silver electrodes.